E nvironmen ental al impac acts o of am amines es an and thei - - PowerPoint PPT Presentation

SINTEF M M aterials and C hemistry

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E nvironmen ental al impac acts o

• f am

amines es an and thei eir d deg egrad adat ation products: C urren ent stat atus an and k knowled edge e gap aps

Andy Bootha, E irik F alck da Silvaa, T

• re Syversenb and O

dd G unnar Brakstada

aSINTE

FMaterials and C hemistry, Dept. Marine E nvironmental T echnology

bInstitutefor Neuromedicine, NTNU

SINTEF M M aterials and C hemistry

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Three m ee mai ain focus ar areas eas for em emissions

E mission profileand concentration Atmospheric transport, processes and deposition T errestrial and aquatic transport, processes and exposure Thes ese e three p ee proces esses es ultimat atel ely det eter ermine w e who (peo eople) e) o

• r what

at (en environmen ent) i is ex exposed ed t to w which chem emical als an and at at which concen entrat ation

SINTEF M M aterials and C hemistry

• Most focus has been on the use
• f ME

A

• An increasing number of

studies are considering other solvent systems

• C
• mputational chemistry and

modellingused to predict ME A degradation products (and

• ther amine solvents)

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C ap apture e plan ant em emissions

1Brakstad, O

. G .; Silva, E . F . d.; Syversen, T . "Support oninput to environmental discharges - E valuationof degradationcomponents," SINTE F , 2010.

• W

ide range of degradation products - ammonia, nitrosamines, nitramines, alkylamines, aldehydes and ketones1

• C
• mpounds of most concern (e.g. nitrosamines) are formed in very small amounts or

thought to form in very small amounts (e.g. nitramines)

• Ther

ere e ar are e curren ently n no em emission s stan andar ards f for C C O

2 cap

apture p e plan ants

SINTEF M M aterials and C hemistry

Atmos

• sph

pheric transpor port and pr proc

• cesses

Atmosphericprocesses3

• Photo-induceddegradation
• C

hemical degradation Local or long distance transport2 Partitioning R ain Aerosols/particles W et deposition Dry deposition

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Emissi ssion

2Berglen, T

. F .; T ønnesen, D.; Dye, C .; Karl, M.; Knudsen, S.; T arrasón, L. "C O 2 T echnology C entre Mongstad – updatedair dispersioncalculations. Updateof O R 12/2008," NorwegianInstitute for Air Research, 2010.

3Bråten, H. B.; Bunkan, A. J.; Bache-

Andreassen, L.; Solimannejad, M.; Nielsen, C .

• J. "Final report on a theoretical study on the

atmospheric degradation of selected amines," NILU, 2009

SINTEF M M aterials and C hemistry

5 CLAY OXIDE OrgMat

T er erres estrial al an and aq aquat atic proces esses es

Per ersisten ence e an and E Exposure e = ƒ ƒ (volat atilisat ation, run-off, leac eaching, c chem emical al reac eaction, b biodeg egrad adat ation, ad adsorption an and u uptak ake) e)

• V
• la

latilis ilisatio ion

• Ru

Run-of

• ff
• Up

Uptake

• Dis

issolu lutio ion an and transpor port

• C

hem emical al reaction/hyd ydrolysi ysis

• Adsor
• rpt

ption

• n
• Biodeg

egrad adat ation

Groundwater

SINTEF M M aterials and C hemistry

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ME A as as an an ex exam ample

O H NH2

SINTEF M M aterials and C hemistry

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E nv nvironm nment nt –ME A E A biod

• deg

egrad adat ation & & ecot

• tox
• x dat

ata

GROUP Degradation product Biodegradability (%)

AEcotoxicity

(EC50 or LC50; mg/L) Nitrosamines N-nitroso-dimethylamine Judged biodegrable 4 (phytoplankton) 4-nitroso-morpholine No data 75 (fish) N-nitroso-diethanolamine No data No data 2-(methyl-nitrosoamino)-ethanol No data No data Nitramines Dimethylnitramine No data No data Amines, amides, aldehydes, ketones Methylamine 55-100 10 (fish) Dimethylamine 30-100 9 (phytoplankton) Ethylamine 98-100 10 Diethanolamine (DEA) 93-97 2 (phytoplankton) N-(2-hydroxyethyl)-formamide (HEF) No data No data N-(2-hydroxy-ethyl)imidazole (HEI) No data No data 2-methylaminoethanol 93 33 (Daphnia) 1,2-Ethanediol or ethyleneglycol (EG) 56 18 (Daphnia) Other compounds Ammonia Nitrification 0.024 (fish) Formaldehyde 90 0.30 (phytoplankton Acetaldehyde 80 31 (fish) Acetone 84-90 2840 (phytoplankton) Formamide 30-100 4600 (fish)

A)Highest ecotoxicity selected from 3 trophic levels

The e quan antity an and qual ality o

• f eq

equival alen ent dat ata a av avai ailab able e for other er s solven ent types es i is usu sually y less ss than f for M MEA

SINTEF M M aterials and C hemistry

• M
• st ter

erres estrial al an and aq aquat atic en environmen ent s studies es h hav ave e focused ed

• n par

aren ent am amines es o

• nly, h

howev ever er:

• A recent study assessed the biodegradability and ecotoxicity of

ME A degradation products using modelling and reported data1

• All compounds with available data appeared to be biodegradable

(30-100% ), whilst ecotoxicity varied significantly

• E

xperimental data is missing for many compounds and compound groups (e.g. nitrosamines and nitramines)

• Some degradation products may persist in the environment due

to low biodegradability, posing a possible risk if accumulated in aquatic systems (e.g. groundw ater).

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T er erres estrial al an and aq aquat atic proces esses es

1Brakstad, O

. G .; Silva, E . F . d.; Syversen, T . "Support oninput to environmental discharges - E valuationof degradationcomponents," SINTE F , 2010.

SINTEF M M aterials and C hemistry

Long-term toxicity

– C –carcinogenicity – M –mutagenicity – R –reproduction toxicity – S –sensitisation

Acute toxicity

– LD

50is the concentration of a chemical which

causes 50% mortality in a population

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Hu Human heal ealth –ME A E A d deg egrad adat ation pr prod

• ducts d

data

GROUP Degradation product Acute LD50 (mg/kg bw) Long-term Occupational exposure limits (OEL – mg/m3) Nitrosamines N-nitroso-dimethylamine < 0.5 (inhalation) CMR 0.001 4-nitroso-morpholine < 0.5 (inhalation) CM(R) 0.001 N-nitroso-diethanolamine >2000 (oral) CM(R) 0.001 2-(methyl-nitrosoamino)- Ethanol No data CM(R)

• Nitramines

Dimethylnitramine 300-2000 (oral) (C)

• Amines, amides,

aldehydes, ketones Methylamine 0.5-20 (inhalation) M 0.13 Dimethylamine 2-10 (inhalation) S 3.5 Ethylamine 50-300 (oral) ? 18 Diethanolamine (DEA) No data ?

• N-(2-hydroxyethyl)- Formamide (HEF)

No data ?

• N-(2-hydroxy-ethyl)imidazole (HEI)

300-2000 (oral) ?

• 2-methylaminoethanol

300-2000 (oral) ? 9.4 1,2-Ethanediol or ethyleneglycol (EG) 300-2000 (oral) R

• Other compounds

Ammonia 0.5-2 (inhalation) (M) 18 Formaldehyde < 0.5 (inhalation) CM(R)S 0.6 Acetaldehyde 300-2000 (oral) CMRS 45 Acetone Negligible

• 295

Formamide 10-20 R 18

Occupational exposure limits (OEL)

– OEL is exposure limits for healthy people – OEL may vary from country to country – OEL used here are the strictest available limits

SINTEF M M aterials and C hemistry

• Human

an heal ealth haz azar ards ar are as e associat ated ed with s sev ever eral al o

• f the

e sugge ggested degr gradation

• n pr

prod

• ducts for
• r M

M E A, h how

• wever:
• Data for many products are not available
• Potential long-term effects associated with mutagenicity,

genotoxicity/carcinogenicity and reproduction effects are documented for specific nitrosamines, volatile aldehydes and alkylamines

• Indicates that nitrosamines may contribute to the health risk of

the population, although their emission concentration is small1

• The real risks cannot be estimated until the fate of these

compounds has been determined

• The

e quan antity an and qual ality o

• f eq

equival alen ent dat ata a av avai ailab able f e for o

• ther

er so solvent typ ypes s is u s usu sually l y less ss than for M M E A

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Hu Human heal ealth

SINTEF M M aterials and C hemistry

• R

A combines the toxicity and ecotoxicity information with the potential fate of the components in the environment

• R

A identifies the concentrations people and the environment are exposed to

• F

ate data (and therefore environmental concentrations) are difficult to predict............but we can use available models (e.g. Q SAR and computational chemistry)

• Need to understand the limitations with using such modelling

methods to generate predicted values

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Ho Howdo

• we

we us usethi his data??? ???

RISK SK A ANAL YSI SIS! S!

SINTEF M M aterials and C hemistry

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C as ase e liter erat ature e study Nitrosam amines es –fat ate i e in t the aq e aquat atic en environmen ent

SINTEF M M aterials and C hemistry

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E P E PISUITE E –Soi

• il adsor
• rpt

ption

• n a

and bioa

• accumulation
• n (

(Q SAR)

Nitrosamine

A)Soil adsorption (Koc) B)Bioaccumulation (log Pow)

N-nitrosodiethanolamine 0.2242

• 1.28

Nitrosopiperidine 12.04 0.7223 Nitrosodiethylamine 14.03 0.48 Nitrosodimethylamine 3.683

• 0.57

Nitroso-N-methylethylamine 8.01 0.04 Nitrosomorpholine 3.528

• 0.44

Nitroso-N-propylamine 43.03 1.36 Nitrosopyrrolidine 5.976

• 0.19

Nitrosopiperazine 2.332

• 1.49

Dinitrosopiperazine 2.332

• 0.85

A) Compounds with Koc values of less than 500 indicate little or no adsorption to soils and are more mobile B) Compounds with log Pow ≥ 3 are regarded as bioaccumulating

• Commercially available suite of nitrosamines (not necessarily amine

degradation products)

• Nitrosamines have low soil/sediment adsorption coefficients and a low

bioaccumulation potential

• Nitrosamines are therefore expected to follow the w

ater flow through soil and surface runoff

SINTEF M M aterials and C hemistry

14 Nitrosamine Biodegradation probability

A)Primary A)Ultimate B)Anaerobic c)Ready biodegradable

N-nitrosodiethanolamine 3.93 (days) 2.84 (weeks) 1.21 (fast) Yes Nitrosopiperidine 3.70 (days-weeks) 2.56 (weeks-months) 0.24 (not fast) No Nitrosodiethylamine 3.72 (days-weeks) 2.59 (weeks-months) 0.73 (fast) No Nitrosodimethylamine 3.76 (days-weeks) 2.66 (weeks-months) 0.68 (fast) No Nitroso-N-methylethylamine 3.74 (days-weeks) 2.62 (weeks-months) 0.70 (fast) No Nitrosomorpholine 3.69 (days-weeks) 2.55 (weeks-months) 0.10 (not fast) No Nitroso-N-propylamine 3.68 (days-weeks) 2.53 (weeks-months) 0.78 (fast) No Nitrosopyrrolidine 3.72 (days-weeks) 2.59 (weeks-months) 0.36 (not fast) No Nitrosopiperazin 3.74 (days-weeks) 2.58 (weeks-months) 0.53 (fast) No Dinitrosopiperazine 3.68 (days-weeks) 2.11 (weeks-months) 0.36 (not fast) No

A) 5=hours; 4=days; 3=weeks; 2=months B) >0.5 = biodegradaes fast C) If the ultimate survey result is ‘weeks’ or faster (i.e. ‘days’ or ‘days-weeks’) the prediction is YES (ready biodegradable). If this

condition is not satisfied, the prediction is NO (not readily biodegradable).

E P E PISUITE E –Biodeg egrad adat ationbas ased ed on

• n Q

S Q SAR ap approac aches es

SINTEF M M aterials and C hemistry

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C

• ncen

entrat ation-dep epen enden ent b biodeg egrad adat ation o

• f

nitrosam amines es

From G G unni nnison n et al., 2000 2000

• Sub mg/L (ppm) concentrations
• f NDMA hadhalf-lives of

approximately 15 days

• Theseconcentrations arestill

significantly abovethose expectedin theenvironment, suggesting evenshorter half- lives

SINTEF M M aterials and C hemistry

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C

• ncen

entrat ation-dep epen enden ent b biodeg egrad adat ation o

• f

nitrosam amines es

• Similar half-lives wereobsevred for a range of nitrosamines studied at thesame

concentration

Fr From Drew ewes es et al., 2006 2006

SINTEF M M aterials and C hemistry

• Photodeg

egrad adat ation is c consider ered ed to b be t e the e most r rap apid (minutes es) deg egrad adat ation proces ess f for n nitrosam amines es pres esen ent in t the at e atmospher ere

• Photodeg

egrad adat ation h hal alf-lives es of 7 n nitrosam amines es i in w at ater er under er C C al alifornia a mids dsummer c condi ditions v varied d be between 11 11 and 16 d 16 minutes

• 99 %

removal of nitrosamines after one hour sunlight exposure

• Photodeg

egrad adat ation in aq aquat atic system ems is d dep epen enden ent on oxygen en an and p pH l lev evel els

• Photodegradation rates higher in aerobic than in anaerobic environment and

vary with pH

• Hyd

ydrolysi ysis: s: Nitrosa samines s are r resi sist stant to hyd ydrolysi ysis u s under a acid a and basi sic con

• ndition
• ns
• 17

No Non-biological al deg egrad adat ation of nitrosam amines es i in aq aquat atic system ems

SINTEF M M aterials and C hemistry

• The c

com

• mpos

position

• n a

and c con

• ncentration
• n of
• f a

amines and d degr gradation

• n pr

prod

• ducts

pres esen ent i in t the em e emissions from a P a PC C C plan ant:

• C

hemical composition and concentration of ME A emissions not fully characterised in C O

2 capture plants

• Individual assessment is required for other solvents and solvent mixtures
• The

e at atmospher eric fat ate an e and t tran ansport o

• f am

amines es an and thei eir d deg egrad adat ation products:

• Atmospheric degradation processes still relatively poorly understood
• Atmospheric transport models allow dispersion of chemicals to be predicted

but must be applied to specific cases (i.e. not general)

• Deposition of amines and degradation products to soil and aquatic

environments is difficult to predict

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Know

• wledge

ge ga gaps ps

SINTEF M M aterials and C hemistry

• The en

e environmen ental al fat ate e of am amines es an and t thei eir deg egrad adat ation products in ter erres estrial al an and aq aquat atic system ems:

• E

nvironmental fate and effects studies require reliable emissions data and atmospheric dispersion and process data

• F
• cus on biodegradation to date, but limited experimental data on hydrolysis

and adsorption (+ other processes)

• Suitable extraction and analytical chemical methods lacking for complex

environmental samples, such as w ater and soil

• Q

SAR approaches may not be very suitable for certain compound groups, and therefore must be improved with experimental data

• The h

e heal ealth ef effec ects of c clas asses es of c compounds ar are e rel elat ativel ely wel ell under erstood from

• m pr

previou

• us studies:
• Specific studies on long-term effects such as carcinogenicity and impaired

reproduction have not been completed for nitrosamines, nitramines and other compounds

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Know

• wledge

ge ga gaps ps

SINTEF M M aterials and C hemistry

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The w e way ay forwar ard

• Accurat

ate em e emissions d dat ata ( a (composition an and concen entrat ation) from C O

2 cap

apture e plan ants is need eeded ed f for a a ran ange o e of s solven ent t types es

• Asse

ssessm ssment of e exp xposu sure ( (no toxi xicity w y without exp xposu sure)

• Persistence in the environment (degradation processes)
• T

ransport in the environment (identification of sinks)

• Bioaccumulation (uptake and storage by organisms including humans)
• Use

e av avai ailab able e toxicity d dat ata t a to det eter ermine e ex exposure e limits f for human ans ( (wher ere e this dat ata a is n not al alread eady av avai ailab able)

• Det

eter ermine e what at the ac e accep eptab able e em emissions lev evel els ar are e using r risk as asses essmen ent E val aluat ation should b be e under ertak aken en at at eac each s step ep t to iden entify i if t ther ere i e is a a need eed t to continue w e with t the e proces esses es

SINTEF M M aterials and C hemistry

Acknow

• wledge

gements: This pu publication

• n for
• rms a

a pa part of

• f t

the B BIG C O 2 pr proj

• ject,

per erformed ed u under er t the e strat ateg egic Norweg egian an res esear earch program am C C

• limit. The au

e author(s) ac acknowled edge t e the p e par artner ers: Stat atoil, G G E G lobal al Res esear earch, Stat atkraf aft, Aker er C C lean ean C arbon

• n, Shell, T

TO T AL, C

• n
• noc
• coP
• Phillips

ps, ALSTO M, t the R Research C

• u
• uncil of
• f N

Nor

• rw

ay (178004/ 178004/I30 30 and 176059/ d 176059/I30) 0) and G d G assnova

Th Thanks!

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Acknowled edgem emen ents